Semiconductor processing method of forming a tantalum oxide containing capacitor

ABSTRACT

A semiconductor processing method of forming a capacitor on a substrate includes, a) providing an oxidizable and electrically conductive inner capacitor plate on the substrate; b) cleaning the inner capacitor plate to remove oxide therefrom; c) within a chemical vapor deposition reactor, chemical vapor depositing a dielectric nitride layer over the cleaned inner capacitor plate to a first thickness, the substrate not being exposed to oxidizing conditions between the cleaning and chemical vapor depositing steps; d) providing a densified Ta 2  O 5  dielectric layer over the dielectric nitride layer; and e) providing an outer capacitor plate over the Ta 2  O 5  layer. Additionally, a method of forming a capacitor on a substrate includes, i) providing an oxidizable and electrically conductive inner capacitor plate on a substrate; ii) providing a densified Ta 2  O 5  dielectric layer over the inner capacitor plate; iii) within a chemical vapor deposition reactor, chemical vapor depositing a dielectric nitride layer over the Ta 2  O 5  layer to a first thickness; and iv) providing an outer capacitor plate over the Ta 2  O 5  layer, the outer capacitor plate being provided outwardly of the dielectric nitride layer. The invention also includes capacitors produced according the method.

TECHNICAL FIELD

This invention relates to semiconductor processing methods of forming capacitors having a Ta₂ O₅ capacitor dielectric layer,

BACKGROUND OF THE INVENTION

As DRAMs increase in memory cell density, there is a continuing challenge to maintain sufficiently high storage capacitance despite decreasing cell area. Additionally, there is a continuing goal to further decrease cell area. One principal way of increasing cell capacitance is through cell structure techniques. Such techniques include three-dimensional cell capacitors, such as trenched or stacked capacitors. Yet as feature size continues to become smaller and smaller, development of improved materials for cell dielectrics as well as the cell structure are important. The feature size of 256 Mb DRAMs will be on the order of 0.25 micron, and conventional dielectrics such as SiO₂ and Si₃ N₄ might not be suitable because of small dielectric constants.

Highly integrated memory devices, such as 256 Mbit DRAMs, are expected to require a very thin dielectric film for the 3-dimensional capacitor of cylindrically stacked or trench structures. To meet this requirement, the capacitor dielectric film thickness will be below 2.5 nm of SiO₂ equivalent thickness. Chemical vapor deposited (CVD) Ta₂ O₅ films are considered to be very promising cell dielectric layers for this purpose, as the dielectric constant of Ta₂ O₅ is approximately three times that of conventional Si₃ N₄ capacitor dielectric layers. However, one drawback associated with Ta₂ O₅ dielectric layers is undesired leakage current characteristics. Accordingly, although Ta₂ O₅ material has inherently higher dielectric properties, as-deposited Ta₂ O₅ typically produces unacceptable results due to leakage current.

Densification of Ta₂ O₅ as deposited has been reported to significantly improve the leakage characteristics of such layers to acceptable levels. Prior art densification of such layers includes exposing the Ta₂ O₅ layer to extreme oxidizing conditions. Undesirably, however, such has a tendency to form an SiO₂ layer intermediate/between the polysilicon and Ta₂ O₅. Further and regardless, a thin SiO₂ layer will also typically inherently form during the Ta₂ O₅ deposition due to the presence of oxygen at the polysilicon layer interface. It would be desirable to remove or eliminate this SiO₂ layer intermediate the Ta₂ O₅ and polysilicon layers, yet allow for such desired densification.

One prior art technique reported includes exposing the polysilicon layer to rapid thermal nitridation prior to subsequent deposition of the Ta₂ O₅ layer. Such are reported by Kamiyama et al., "Ultrathin Tantalum Oxide Capacitor Dielectric Layers Fabricated Using Rapid Thermal Nitridation prior to Low Pressure Chemical Vapor Deposition", J. Electrochem. Soc., Vol. 140, No. 6, June 1993 and Kamiyama et al., "Highly Reliable 2.5 nm Ta₂ O₅ Capacitor Process Technology for 256 Mbit DRAMs", 830-IEDM 91, pp. 32.2.1-32.2.4. Such rapid thermal nitridation includes exposing the subject polysilicon layer to temperatures of from 800° C. to 1100° C. for sixty seconds in an ammonia atmosphere at atmospheric pressure. The nitride layer acts as a barrier layer to oxidation during Ta₂ O₅ deposition and subsequent high temperature densification processes to prevent oxidation of the underlying polysilicon electrode. These processes do however have several drawbacks, including the undesired high temperature cycling and formation of a fairly thick native SiO₂ on the nitride in series with the Ta₂ O₅, all of which adversely effects the realization of high capacitance promised by inherent Ta₂ O₅ layers.

It would be desirable to improve upon such prior art processes enabling utilization of Ta₂ O₅ layers in capacitor constructions.

BRIEF DESCRIPTION OF THE DRAWINGS

Preferred embodiments of the invention are described below with reference to the following accompanying drawings.

FIG. 1 is a diagrammatic fragmentary sectional view of a semiconductor wafer fragment at one processing step in accordance with the invention.

FIG. 2 is a view of the FIG. 1 wafer at a processing step subsequent to that shown by FIG. 1.

FIG. 3 is a view of the FIG. 1 wafer at a processing step subsequent to that shown by FIG. 2.

FIG. 4 is a view of the FIG. 1 wafer at a processing step subsequent to that shown by FIG. 3. FIG. is a view of the FIG. 1 wafer at a processing step subsequent to that shown by FIG. 4.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

This disclosure of the invention is submitted in furtherance of the constitutional purposes of the U.S. Patent Laws "to promote the progress of science and useful arts" (Article 1, Section 8).

In accordance with one aspect of the invention, a semiconductor processing method of forming a capacitor on a substrate comprises the following steps:

providing an oxidizable and electrically conductive inner capacitor plate on the substrate;

cleaning the inner capacitor plate to remove oxide therefrom;

within a chemical vapor deposition reactor, chemical vapor depositing a dielectric nitride layer over the cleaned inner capacitor plate to a first thickness, the substrate not being exposed to oxidizing conditions between the cleaning and chemical vapor depositing steps;

providing a densified Ta₂ O₅ dielectric layer over the dielectric nitride layer; and

providing an outer capacitor plate over the Ta₂ O₅ layer.

In accordance with another aspect of the invention, a semiconductor processing method of forming a capacitor on a substrate comprises the following steps:

providing an oxidizable and electrically conductive inner capacitor plate on the substrate;

providing a densified Ta₂ O₅ dielectric layer over the inner capacitor plate;

within a chemical vapor deposition reactor, chemical vapor depositing a dielectric nitride layer over the Ta₂ O₅ layer to a first thickness; and

providing an outer capacitor plate over the Ta₂ O₅ layer, the outer capacitor plate being provided outwardly of the dielectric nitride layer.

In accordance with still a further aspect of the invention, a semiconductor processing method of forming a capacitor on a substrate comprises the following steps:

providing an oxidizable and electrically conductive inner capacitor plate on the substrate;

cleaning the inner capacitor plate to remove oxide therefrom;

within a chemical vapor deposition reactor, first chemical vapor depositing a first dielectric nitride layer over the cleaned inner capacitor plate to a first thickness, the substrate not being exposed to oxidizing conditions between the cleaning and first chemical vapor depositing steps;

providing a densified Ta₂ O₅ dielectric layer over the dielectric nitride layer;

within a chemical vapor deposition reactor, second chemical vapor depositing a second dielectric nitride layer over the Ta₂ O₅ layer to a second thickness; and

providing an outer capacitor plate over the Ta₂ O₅ layer, the outer capacitor plate being provided outwardly of the second dielectric nitride layer.

More particularly and first with reference to FIG. 1, a semiconductor wafer fragment in process is indicated generally with reference numeral 10. Such comprises a bulk silicon substrate 12 having a conductive diffusion layer 14 formed therein. An insulating layer 16, typically borophosphosilicate glass (BPSG), is provided over bulk substrate 12. Preferably, an intervening barrier layer 13 is provided intermediate layer 16 and substrate 12 to prevent boron and phosphorus diffusion from layer 16 into substrate 12. A contact opening 18 is provided to diffusion area 14. A conductive material 20 fills contact opening 18, with material 20 and oxide layer 16 having been planarized as shown. Material 20 might be any suitable conductive material, such as tungsten or conductively doped polysilicon. A capacitor construction will be provided atop layer 16 and plug 20, with conductive plug 20 constituting a node to which electrical connection to the capacitor will be made.

An oxidizable and electrically conductive inner capacitor plate layer 22 is provided relative to the illustrated substrate. Such preferable comprises conductively doped polysilicon having a conductivity doping of at least 5×10¹⁹ ions/cm³. For 256 Mb integration, a preferred thickness for layer 22 is from 300 Angstroms to 500 Angstroms. An undesired native silicon oxide layer 24 typically forms atop polysilicon layer 22 upon any exposure of the substrate to oxidizing conditions. Inner capacitor plate layer 22 is subsequently cleaned to remove oxide layer 24, or other potentially entrained contaminants, therefrom. The preferred method for such cleaning is within a chemical vapor deposition reactor utilizing HF vapor. Alternately by way of example, cleaning can occur ex situ of a chemical vapor deposition reactor with the wafer not being subject to temperature and oxygen ambient conditions which would result in reoxidation of layer 22.

Referring to FIG. 2 after layer 24 removal, and within a chemical vapor deposition reactor, a first dielectric nitride layer 26 is first chemical vapor deposited over cleaned inner capacitor plate 22 to a desired first thickness. The illustrated substrate is not exposed to any oxidizing conditions between the previous cleaning and subsequent chemical vapor depositing steps. Ideally, the cleaning and chemical vapor depositing steps are conducted in the same reactor without removing the substrate from the reactor between the cleaning and chemical vapor depositing steps. Example conditions for depositing layer 26 include combination of dichlorosilane gas, a carrier gas and ammonia gas within the reactor, with the wafer temperature being maintained at from 600° C. to 800° C, with the reactor ambient being, maintained at a pressure of from 100 mTorr-500 mTorr. Such will result in deposition of the preferred dielectric nitride material of Si₃ N₄. Preferably, layer 26 is provided as thin as practical, at less than about 30 Angstroms. Ideally, the thickness of layer 26 will be provided at 20 Angstroms, with around 15 Angstroms believed to be most preferred.

Referring to FIG. 3, a Ta₂ O₅ capacitor dielectric layer 28 is chemical vapor deposited over dielectric nitride layer 26, and accordingly also over inner capacitor plate 22. An example process for depositing layer 28 is by low pressure chemical vapor deposition at 450° C. using Ta(OC₂ H₅)₅ and oxygen as precursors. Ta(OC₂ H₅)₅ can be vaporized at 170° C., and introduced into a chemical vapor deposition reactor chamber using argon or another suitable carrier gas. Subsequently, densification by rapid thermal annealing in a dry oxygen atmosphere at a temperature ranging from 700° C. to 900° C. is utilized. An example and preferred thickness for layer 28 in accordance with 256 Mb integration is 100 Angstroms. The annealing of the Ta₂ O₅ layer densifies such layer, with first dielectric nitride layer 26 restricting oxidation of underlying oxidizable inner capacitor plate 22 during the annealing.

Accordingly, such provides a preferred method in accordance with the invention of providing a densified Ta₂ O₅ dielectric layer over nitride layer 24 and inner capacitor plate 22. In this regard, the invention provides improvements over the prior art by minimizing the high temperature cycling which otherwise is required for the prior art rapid thermal nitridation to achieve an oxidation barrier layer intermediate the polysilicon and Ta₂ O₅ layers. Further, provision of a nitride layer by chemical vapor deposition and in accordance with the invention obviates or at least minimizes any native oxide that might be formed intermediate nitride layer 26 in Ta₂ O₅ layer 28 during the deposition. The prior art rapid thermal nitridation provides a considerably thicker and undesired layer of SiO₂ intermediate the Ta₂ O₅ and polysilicon layers.

Referring to FIG. 4 and within a chemical deposition reactor, a second dielectric nitride layer 30 is second chemical vapor deposited over Ta₂ O₅ layer 28 to a desired second thickness. Again preferably, second dielectric nitride layer 30 is provided in the same manner which the first dielectric nitride layer is provided, and to the same preferred thickness.

Referring to FIG. 5, an electrically conductive outer capacitor plate layer 32 is provided over second nitride layer 30, and thus over Ta₂ O₅ layer 28. An example and preferred material is conductively doped polysilicon deposited to a thickness of 500 Angstroms for 256 Mb integration. The illustrated layers 32, 30, 28, 26 and 22 of FIG. 5 would subsequently be patterned, typically in a common masking step, to define a discrete capacitor construction. Providing nitride layer 30 by chemical vapor deposition provides an advantage over the prior art of preventing oxidation of electrode 32 during subsequent heat treatment inherent in the processing to produce a capacitor construction, similar to the advantage layer 26 provides by impeding oxidation of layer 22.

The invention contemplates alternate provision of nitride layers 26 and 30 by alternate means or elimination of one of such layers, with the invention only being limited by the accompanying claims appropriately interpreted in accordance with the doctrine of equivalents.

In compliance with the statute, the invention has been described in language more or less specific as to structural and methodical features. It is to be understood, however, that the invention is not limited to the specific features shown and described, since the means herein disclosed comprise preferred forms of putting the invention into effect. The invention is, therefore, claimed in any of its forms or modifications within the proper scope of the appended claims appropriately interpreted in accordance with the doctrine of equivalents. 

I claim:
 1. A semiconductor processing method of forming a capacitor on a substrate comprising the following steps:providing an oxidizable and electrically conductive inner capacitor plate on the substrate; cleaning the inner capacitor plate to remove oxide therefrom; within a chemical vapor deposition reactor, first chemical vapor depositing a dielectric nitride layer over the cleaned inner capacitor plate to a first thickness, the substrate not being exposed to oxidizing conditions between the cleaning and chemical vapor depositing steps; separately second chemical vapor depositing a Ta₂ O₅ dielectric layer over the first chemical vapor deposited dielectric nitride layer; annealing the Ta₂ O₅ layer to densify such layer, the first chemical vapor deposited dielectric nitride layer restricting oxidation of the underlying oxidizable inner capacitor plate during the annealing; and providing an outer capacitor plate over the Ta₂ O₅ layer.
 2. The semiconductor processing method of forming a capacitor of claim 1 wherein the first thickness is less than about 30 Angstroms.
 3. The semiconductor processing method of forming a capacitor of claim 1 wherein the first thickness is less than about 20 Angstroms.
 4. The semiconductor processing method of forming a capacitor of claim 1 wherein the dielectric nitride comprises Si₃ N₄.
 5. The semiconductor processing method of forming a capacitor of claim 1 wherein the cleaning step comprises vapor cleaning the inner capacitor plate.
 6. The semiconductor processing method of forming a capacitor of claim 1 wherein the cleaning step comprises vapor cleaning the inner capacitor plate, and the cleaning and chemical vapor depositing steps are conducted in the same reactor without removing the substrate from the reactor between the cleaning and chemical vapor depositing steps.
 7. A semiconductor processing method of forming a capacitor on a substrate comprising the following steps:providing an oxidizable and electrically conductive inner capacitor plate on the substrate; cleaning the inner capacitor plate to remove oxide therefrom; within a chemical vapor deposition reactor, chemical vapor depositing a dielectric nitride layer over the cleaned inner capacitor plate to a first thickness, the substrate not being exposed to oxidizing conditions between the cleaning and chemical vapor depositing steps; after the chemical vapor depositing of the dielectric nitride layer, forming a densified Ta₂ O₅ dielectric layer over the chemical vapor deposited dielectric nitride layer; and providing an outer capacitor plate over the Ta₂ O₅ layer.
 8. The semiconductor processing method of forming a capacitor of claim 7 wherein the first thickness is less than about 30 Angstroms.
 9. The semiconductor processing method of forming a capacitor of claim 7 wherein the first thickness is less than about 20 Angstroms.
 10. The semiconductor processing method of forming a capacitor of claim 7 wherein the dielectric nitride comprises Si₃ N₄.
 11. The semiconductor processing method of forming a capacitor of claim 7 wherein the cleaning step comprises vapor cleaning the inner capacitor plate.
 12. The semiconductor processing method of forming a capacitor of claim 7 wherein the cleaning step comprises vapor cleaning the inner capacitor plate, and the cleaning and chemical vapor depositing steps are conducted in the same reactor without removing the substrate from the reactor between the cleaning and chemical vapor depositing steps.
 13. A semiconductor processing method of forming a capacitor on a substrate comprising the following steps:providing an oxidizable and electrically conductive inner capacitor plate on the substrate; chemical vapor depositing a first dielectric nitride layer over the inner capacitor plate; providing a densified Ta₂ O₅ dielectric layer over the first dielectric nitride layer; within a chemical vapor deposition reactor, chemical vapor depositing a dielectric nitride layer over the Ta₂ O₅ layer to a first thickness; and providing an outer capacitor plate over the Ta₂ O₅ layer, the outer capacitor plate being provided outwardly of the dielectric nitride layer.
 14. The semiconductor processing method of forming a capacitor of claim 13 wherein the first thickness is less than about 30 Angstroms.
 15. The semiconductor processing method of forming a capacitor of claim 13 wherein the first thickness is less than about 20 Angstroms.
 16. The semiconductor processing method of forming a capacitor of claim 13 wherein the dielectric nitride comprises Si₃ N₄.
 17. A semiconductor processing method of forming a capacitor on a substrate comprising the following steps:providing an oxidizable and electrically conductive inner capacitor plate on the substrate; cleaning the inner capacitor plate to remove oxide therefrom; within a chemical vapor deposition reactor, first chemical vapor depositing a first dielectric nitride layer over the cleaned inner capacitor plate to a first thickness, the substrate not being exposed to oxidizing conditions between the cleaning and first chemical vapor depositing steps; forming a separate densified Ta₂ O₅ dielectric layer over the first dielectric nitride layer; within a chemical vapor deposition reactor, second chemical vapor depositing a second dielectric nitride layer over the Ta₂ O₅ layer to a second thickness; and providing an outer capacitor plate over the Ta₂ O₅ layer, the outer capacitor plate being provided outwardly of the second dielectric nitride layer.
 18. The semiconductor processing method of forming a capacitor of claim 17 wherein the first and second thicknesses are less than about 30 Angstroms.
 19. The semiconductor processing method of forming a capacitor of claim 17 wherein the first and second thicknesses are less than about 20 Angstroms.
 20. The semiconductor processing method of forming a capacitor of claim 17 wherein the first and second dielectric nitride layers comprise Si₃ N₄.
 21. The semiconductor processing method of forming a capacitor of claim 17 wherein the cleaning step comprises vapor cleaning the inner capacitor plate.
 22. The semiconductor processing method of forming a capacitor of claim 17 wherein the cleaning step comprises vapor cleaning the inner capacitor plate, and the cleaning and first chemical vapor depositing steps are conducted in the same reactor without removing the substrate from the reactor between the cleaning and first chemical vapor depositing steps.
 23. A semiconductor processing method of forming a capacitor on a substrate comprising the following steps:providing an oxidizable and electrically conductive inner capacitor plate on the substrate; cleaning the inner capacitor plate to remove oxide therefrom; within a chemical vapor deposition reactor, first chemical vapor depositing a first dielectric nitride layer over the cleaned inner capacitor plate to a first thickness, the substrate not being exposed to oxidizing conditions between the cleaning and first chemical vapor depositing steps; forming a separate Ta₂ O₅ dielectric layer over the first dielectric nitride layer; annealing the Ta₂ O₅ layer to densify such layer, the first dielectric nitride layer restricting oxidation of the underlying oxidizable inner capacitor plate during the annealing; within a chemical vapor deposition reactor, second chemical vapor depositing a second dielectric nitride layer over the Ta₂ O₅ layer to a second thickness; and providing an outer capacitor plate over the Ta₂ O₅ layer, the outer capacitor plate being provided outwardly of the second dielectric nitride layer.
 24. The semiconductor processing method of forming a capacitor of claim 23 wherein the first and second thicknesses are less than about 30 Angstroms.
 25. The semiconductor processing method of forming a capacitor of claim 23 wherein the first and second thicknesses are less than about 20 Angstroms.
 26. The semiconductor processing method of forming a capacitor of claim 23 wherein the first and second dielectric nitride layers comprise Si₃ N₄.
 27. The semiconductor processing method of forming a capacitor of claim 23 wherein the cleaning step comprises vapor cleaning the inner capacitor plate.
 28. The semiconductor processing method of forming a capacitor of claim 23 wherein the cleaning step comprises vapor cleaning the inner capacitor plate, and the cleaning and first chemical vapor depositing steps are conducted in the same reactor without removing the substrate from the reactor between the cleaning and first chemical vapor depositing steps. 